Chemical production processes and systems

ABSTRACT

Chemical Production Processes and Systems. Chemical production processes are provided that include replacing a halogen of an unsaturated halocarbon to produce an unsaturated hydrohalocarbon. Chemical production systems are provided that include a reaction zone coupled to first and second reservoirs, the first reservoir containing an unsaturated halocarbon and the second reservoir containing a hydrogenating reagent with the system being configured to expose the unsaturated halocarbon of the first reservoir to the hydrogenating agent of the second reservoir within the reaction zone.

RELATED PATENT DATA

This application is a 35 U.S.C. §371 of and claims priority to PCTInternational Application Number PCT/U52005/030349 which was filed 26Aug., 2005 , and was published in English, which claims priority under35 U.S.C. §119 to U.S. Provisional Patent Application No. 60/605,232which was filed 26 Aug., 2004 the entirety of each are incorporatedherein by reference.

TECHNICAL FIELD

The present invention relates to the field of chemical productionprocesses and systems and more specifically to the production ofhydrogenated olefins.

BACKGROUND

Hydrogenated olefins can be produced in numerous ways, including viaelimination reactions for example. Hydrogenating an olefin, particularlyhalogenated olefins, can prove to be difficult for at least the reasonthat the drawback of hydrogenating an olefin is that the hydrogenstypically add across the double bond saturating the compound. It can bebeneficial to be able to add a hydrogen to an olefin without saturatingthe compound. The present invention provides chemical productionprocesses and systems for hydrogenating olefins.

SUMMARY

Chemical production processes are provided that include replacing ahalogen of an unsaturated halocarbon to produce an unsaturatedhydrohalocarbon.

Chemical production systems are provided that include a reaction zonecoupled to first and second reservoirs, the first reservoir containingan unsaturated halocarbon and the second reservoir containing ahydrogenating reagent with the system being configured to expose theunsaturated halocarbon of the first reservoir to the hydrogenating agentof the second reservoir within the reaction zone.

BRIEF DESCRIPTION OF THE FIGURE

The figure is an exemplary system for preparing compositions accordingto an embodiment.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Chemical production processes and systems as described with reference tothe Figure depicting a system 10 that includes a reaction zone 11coupled to a halocarbon reservoir 12 and a hydrogenating reagentreservoir 13. System 10 further includes a product recovery reservoir14.

The halocarbon of reservoir 12 can be a C-2 halocarbon, and in exemplaryembodiments, the halocarbon can be a heterohalocarbon. For example, andby way of example only, the halocarbon can comprise both F and Cl, and,as another example, the halocarbon can comprise both F and Br. Inexemplary embodiments, the halocarbon can also be

for example.

According to exemplary embodiments, the hydrogenating reagent fromhydrogenating reagent reservoir 13 can be provided to reaction zone 11.According to exemplary embodiments, the hydrogenating reagent mayinclude H, such as H₂. Reaction zone 11 can be coupled to reservoirs 13and 14 via separate conduits with each conduit configured to control theflow of the contents of the reservoirs to reaction zone 11. The conduitsmay be equipped with flow meters, for example. Both the halocarbon andthe hydrogenating reagent may be provided to the reaction zone at a moleratio of hydrogenating reagent to halocarbon utilizing the flow meters.For example, the mole ratio of hydrogenating reagent to halocarbon maybe from about 0.66 to about 11. By way of another example, the moleratio may be at least about 0.66 and/or the mole ratio may be less than11. In another exemplary embodiment, the mole ratio may be at leastabout 1.8.

Reaction zone 11 can include a single and/or multiple reactors. Areactor within reaction zone 11 can be constructed of a nickel-alloysuch as an Inconel® (Tevo Industries 9337 Ravenna Rd. Twinsburg, Ohio44087) tube having a volume of 34 cc (OD=0.5″, length=14.125″, wallthickness=0.035″) equipped with a pressure gauge, pressure relief valve,Matheson Gas rotometers for gas feeds, and/or a vaporizer, for example.

Reaction zone 11 may include a catalyst composition within a reactor.The catalyst composition may comprise a catalyst support and/or thecatalyst composition may comprise activated carbon. The catalystcomposition provided within reaction zone 11 may comprise one or morePd, Cu, and/or Ni and/or the catalyst composition may comprise both Pdand Cu. Where the catalyst composition comprises both Pd and Cu, thecomposition may include at least about 0.6% (wt./wt.) Pd and/or thecomposition may be at least about 5.5% (wt./wt.) Cu. In accordance withother embodiments, the catalyst composition may comprise nickel andnickel may be at least about 5% (wt./wt.) of the composition. Additionalcatalyst compositions can include:; Pricat CZ 29/4, Al₂O₃, ZnO, CuO,(Synetix (PO Box 1, Billingham, Cleveland, TS23 1 LB, UK); 7% FeCl₃ onTakeda Carbon (Life-Environment Company, 12-10, Nlhonbashi 2-chamoChuo-ku, Tokyo 103-8868, Japan); FeCl₃ (in-house,and/or ZnCl₂(in-house); and those obtained from Engelhard (Chemical Catalysts Group,554 Engelhard Drive, Seneca, S.C. 29678), such as,0.6% Pd/5.5% Cu and/orNi (Engelhard, 5% Ni on 1.5 mm carbon).

Prior to providing the halocarbon and/or the hydrogenating agent fromreservoirs 12 and 13, respectively, a reactor of reaction zone 11 may bepacked with the catalyst composition and heated to a temperature and/orexposed to a reducing agent for a sufficient time to activate thecatalyst composition. Activation of the catalyst composition may beperformed over a period of from about an hour to about 24 hours, forexample. Typically, the catalyst composition within the reactor may beheated to from about 150° C. to about 300° C. during the activation. Thecatalyst composition may also be re-activated intermittently during theprocess at temperatures of from about 150° C. to 400° C.

The halocarbon and hydrogenating reagent may be formed into a mixturewithin the reactor and a portion of the mixture may be heated to atleast 300° C. According to an exemplary embodiment, the portion may beheated to from about 300° C. and to about 400° C. The portion may alsobe heated to greater than about 400° C., for example. The temperaturewithin the reaction zone can also be from 150° C. to 475° C. whenproviding mole ratios of reducing-reagent to halocarbon of 0.1 to 10.0.The reactants can reside within reaction zone 11 to provide contacttimes of from about 2 to about 20 seconds and reducing-reagent flowrates can be from 25-100 cc/min while the halocarbon flow. rates can befrom 8-410 cc/min.

Products leaving the reactor can be captured and/or further processedwithin product recovery reservoir 14. Reservoir 14 can include anapparatus such as a 10% KOH scrubber, a Drierite tube, and/or a dry ice/acetone trap, for example. Exemplary products include, but are notlimited to, unsaturated hydrohalocarbons including C-2 hydrohalocarbons.For example, and by way of example only, the hydrohalocarbon cancomprise both F and H. In exemplary embodiments, the hydrohalocarbon canbe trifluoroethylene (C₂F₃H, TriFE), and/or

for example. As such system 10 can be used to replace a halogen of anunsaturated halocarbon to produce an unsaturated hydrohalocarbon.

Exemplary schemes 1 and 2 demonstrate exemplary reactions that can beperformed utilizing system 10 of the Figure.

According to scheme (1) above, an Inconel tube can be packed with 0.6%Pd/5.5% Cu catalyst on activated carbon and maintained at 400° C. Thereactants can be provided to the tube at a 4.5 mole ratio of H₂ to CTFEand exposed to the catalyst for a 9.6 second contact time. Theconversion of CTFE to TriFE can be about 30.3% and selectivity can be83.5% as determined by gas chromatography.

According to another embodiment, the Inconel tube can be packed with aNi (Engelhard, 5% Ni on 1.5 mm carbon) catalyst and maintained at 350°C. The reactants can be provided to the tube at a 0.66 mole ratio of H₂to CTFE and exposed to the catalyst for an 11.2 second contact time. Theconversion of CTFE to TriFE can be about 50.1% and the selectivity canbe 61.1% as determined by gas chromatography.

According to scheme (2) above, an Inconel tube can be packed with the0.6% Pd/5.5% Cu catalyst on activated carbon and maintained at 300° C.The reactants can be provided to the tube at a 4.5 mole ratio of H₂ toBTFE and can be exposed to the catalyst for a 19.6 second contact time.The conversion of BTFE to TriFE can be 72.3% and selectivity can be87.0% as determined by gas chromatography.

According to still another embodiment, an Inconel tube can be packedwith the Ni (Engelhard, 5% Ni on 1.5 mm carbon) catalyst and maintainedat 400° C. The reactants can be provided to the tube at a 1.8 mole ratioof H₂ to BTFE and can be exposed to the catalyst for a 12.9 secondcontact time. The conversion of BTFE to TriFE can be 96.8% andselectivity can be 90.7% as determined by gas chromatography.

1. A chemical production process comprising replacing one or both of aCl and a Br of one or both of C₂F₃Cl and C₂F₃Br in the presence of botha hydrogenating reagent and a catalyst comprising Cu and Pd to producean unsaturated hydrohalocarbon, the catalyst comprising Cu at a weightpercent greater than a weight percent of Pd.
 2. The chemical productionprocess of claim 1 wherein the replacing comprises: providing thehalocarbon to within a reactor; providing a hydrogenating reagent towithin the reactor; and recovering the hydrohalocarbon from the reactor.3. The chemical production process of claim 2 wherein the halocarbon andthe hydrogenating reagent are provided to within the reactor at a moleratio of hydrogenating reagent to halocarbon, the mole ratio being fromabout 0.1 to about
 11. 4. The chemical production process of claim 2wherein the one or both of C₂F₃Cl and C₂F₃Br and the hydrogenatingreagent are provided to within the reactor at a mole ratio ofhydrogenating reagent to one or both of C₂F₃Cl and C₂F₃Br, the moleratio being at least 0.1.
 5. The chemical production process of claim 2wherein the one or both of C₂F₃Cl and C₂F₃Br and the hydrogenatingreagent are provided to within the reactor at a mole ratio ofhydrogenating reagent to one or both of C₂F₃Cl and C₂F₃Br, the moleratio being less than
 11. 6. The chemical production process of claim 2wherein the one or both of C₂F₃Cl and C₂F₃Br and the hydrogenatingreagent are provided to within the reactor at a mole ratio ofhydrogenating reagent to one or both of C₂F₃Cl and C₂F₃Br, the moleratio being at least 1.8.
 7. The chemical production process of claim 2wherein the hydrogenating reagent comprises H.
 8. The chemicalproduction process of claim 2 wherein the hydrogenating reagent is H₂.9. The chemical production process of claim 2 further comprisingproviding a catalyst composition to within the reactor.
 10. The chemicalproduction process of claim 9 wherein the catalyst composition comprisesa catalyst support.
 11. The chemical production process of claim 9wherein the catalyst composition comprises activated carbon.
 12. Thechemical production process of claim 1 wherein the Pd is at least about0.6% (wt./wt.) of the catalyst.
 13. The chemical production process ofclaim 1 wherein the Cu is at least about 5.5% (wt./wt.) of the catalyst.14. The chemical production process of claim 2 wherein the reactor isconstructed of a nickel alloy.
 15. The chemical production process ofclaim 2 further comprising: forming a mixture comprising the halocarbonand the hydrogenating reagent within the reactor; and heating a portionof the mixture to at least about 475° C.
 16. The chemical productionprocess of claim 2 further comprising: forming a mixture comprising theone or both of C₂F₃Cl and C₂F₃Br and the hydrogenating reagent withinthe reactor; and heating a portion of the mixture to from about 150° C.to about 400° C.
 17. The chemical production process of claim 2 furthercomprising: forming a mixture comprising the one or both of C₂F₃Cl andC₂F₃Br and the hydrogenating reagent within the reactor; and heating aportion of the mixture to at least about 400° C.
 18. The chemicalproduction process of claim 2 further comprising: forming a mixturecomprising the one or both of C₂F₃Cl and C₂F₃Br and the hydrogenatingreagent within the reactor; and heating a portion of the mixture to atleast about 300° C.
 19. The chemical production process of claim 2further comprising: forming a mixture comprising the one or both ofC₂F₃Cl and C₂F₃Br and the hydrogenating reagent within the reactor; andheating a portion of the mixture to from about 300° C. to about 400° C.